Azo dyestuffs



United States Patent 3,139,422 AZO DYESTUFFS Gerald Booth, George TrappDouglas, James Stuart Hunter, and Eric Leslie Johnson, Manchester,England, assignors to Imperial Chemical Industries Limited, Millbank,London, England, a corporation of Great Britain No Drawing. Originalapplication Oct. 11, 1961, Ser. No. 144,319. Divided and thisapplication Mar. 25, 1963, Ser. No. 267,764 Claims priority, applicationGreat Britain Oct. 4, 1957 1 Claim. (Cl. 260-158) This application is adivisional application of application Serial No. 144,319, which wasfiled in the United States on October 11, 1961, and which is acontinuationin-part application of application Serial No. 762,924, filedin the United States on September 24, 1958, now abandoned, and relatesto new azo dyestuffs and more particularly to new water-insoluble azodyestufis valuable for the colouration of textile materials.

By water-insoluble azo dyestuffs is meant, as will be understood bythose skilled in the art, dyestuffs which are free fromwater-solubilising groups. Water-solubilising groups which are typicallypresent in water-soluble azo dyestuffs are sulphonic acid, carboxylicacid and acyl sulphonamido groups. Such water-solubilising groups arenot present in the water-insoluble dyestuffs of our invention. It willbe recognised, of course, that these watersolubilising groups are allessentially acidic groups, and will form salts if a dyestuif containingthe same is placed in an aqueous alkaline medium. Accordingly, it willbe understood that the term water-insoluble azo dyest r is used hereinin its conventional sense as meaning that there is no such sulphonicacid, carboxylic acid or acyl sulphonamido groups, or salts, of suchgroups, in the dyestuif molecule.

The new water-insoluble azo dyestuffs of our invention containsulphonarnido groups in which one or both of the hydrogen atoms havebeen replaced by certain chloroalkyl or bromoalkyl groups. We have foundthat the new dyestuffs are superior, especially when applied topolyamide textile materials, to the azo dyestuffs already known in thatthey have good build-up properties and give colourations ofexceptionally high fastness to wet treatments. Colourations obtained ontextile materials such as polyamide textile materials with dispersedyestuffs are in general deficient in fastness to wet treatments, butthe colourations obtained with the new disperse azo dyestuffs of thepresent invention on textile materials comprising fibres such as wool,silk, regenerated protein fibres, polyamide fibres or basically modifiedpolyacrylonitrile fibres have excellent fastness to wet treatments notonly in that they retain their strength of shade but also in that theyshow very little staining of adjacent textile materials.

The known disperse azo dyestuffs do not react chemically with textilefibres. When however the new azo dyestufis are applied to textilematerials comprising fibres such as wool, silk, regenerated protein,polyamide or basically modified polyacrylonitrile fibres a chemical bondis formed between the dyestuif and the textile fibre. It seems probablethat the increased fastness of the new dyestufis is due at least in partto chemical combination with the fibre in this way. Since the process ofdyeing with the new dyestuffs is in reality a chemical reaction betweenthe dyestuif on the one hand, and the textile on the other, it isentirely surprising to find that the new dyestuffs not only haveimproved fastness properties but that they also give quite leveldyeing's on textile fibres, particularly polyamide fibres.

The new water-insoluble azo dyestufis of the invention are of theformula wherein A is a radical selected from the group consisting ofphenyl, naphthyl, thiazolyl and benzthiazolyl radicals,

A is a radical selected from the group consisting of phenyl and naphthylradicals,

A" is a radical selected from the group consisting of phenyl, naphthyl,pyrazolonyl, and acetoacetylaminophenyl radical, said dyestuffscontaining at most one group of the formula lower alkyl, bromo loweralkyl, chlorohydroxy lowerakyl, bromohydroxy lower alkyl,chlorocyclohexyl, bromocyclohexyl, hydroxy lower alkyl, ethoxy loweralkyl, and a benzene radical; and

R and R together form with the nitrogen atom, N, a heterocyclic ringselected from the class consisting of pyrrolidine, alkylpyrrolidine, andpiperidine, which heterocyclic ring contains a halogen atom selectedfrom the class consisting of chlorine and bromine;

provided that when m is 2 the two SO NRR' groups present in the azodyestuif are attached to different radicals represented by A.

The double bond in the group of the formula may be an aromatic oraliphatic double bond, and thus the hydroxyl radical in the said groupmay be a phenolic hydroxyl radical or an enolic hydroxyl radical. Whenan enolic hydroxyl radical is present the compound may also exist in theketonic form. Included within the scope of the invention therefore aredyestufis which contain at most one monohydroxybenzene,monohydroxynaphthalene or monohydroxybenzthiazole radical, or at mostone pyrazolonyl or acetoacetylaminophenyl radical.

It will be understood that the term lower alkyl used in defining R and Rabove indicates an alkyl radical of not more than 4 carbon atoms.

Specifically the fi-bromo and fi-chloro lower alkyl groups representedby R may be for example B-chloroethyl, {3- bromoethyl, B-chloropropyl,B-bromopropyl, 'y chloroprop-fl-yl, or u-ChIOIObUt-fl-Yl groups; the*y-chloro and bromo-substituted 8-hydroxy lower alkyl groups may be forexample 'y-chloro-fi-hydroxypropyl or 'y-bromo-fl-hydroxypropyl groups;and the fiz'y-dichloro substituted lower alkyl groups may be for examplepz'y-dichloropropyl, or fiz'y-dibromopropyl groups.

Specifically also we may mention the following as examples of theradicals represented by R:

fl-Chloroethyl, B-bromoethyl, fl-chloropropyl, fl-bromopropyl,'y-chloro-fl-hydroxypropyl, 'y-bromo-B hydroxypropyl,Z-chlorocyclohexyl, methyl, ethyl, propyl, 3-hydroxyethyl,fi-ethoxyethyl. The term benzene radical used in the definition of Rincludes not only the phenyl radical, but also substituted phenylradicals such as tolyl,

chlorophenyl, methoxyphenyl and acetylaminophenyl. As

examples of heterocyclic rings containing a chlorine or bromine atom,and together formed from the groups R, R and a nitrogen atom, there maybe mentioned chloro and 3,1 '2 .3 bromo derivatives of pyrrolidine forexample 3-ch1oropyrrolidine and piperidine derivatives such as 3-chloroand 3-bromo piperidine.

The different radicals represented by A in the new water-insoluble azodyestuffs may carry other substituents in addition to the SO NRR' group.As examples of such substituents there may be mentioned alkyl, forexample methyl, alkoxy, for example methoxy, halogen, for example chloroor bromo, alkylsulphonyl, for example methylsulphonyl or ethylsulphonyl,cyano, trifluoromethyl, dialkylamino, for example dirnethylamino ordiethylamino, acylamino, for example acetylamino, and carbalkoxy, forexample carbomethoxy.

The dyestuffs of the invention may be manufactured by diazotising anamine of the formula ANH or wherein A and A have the meanings statedabove, coupling the diazo compound so obtained with a couplingcomponent, the amine and the coupling component being so chosen that theresultant azo dyestufiis water-insoluble as aforesaid and contains atmost one radical of the formula and contains one or two groups of theformula SO NRR where R and R have the meanings stated above, each of thesaid groups being attached to a different aryl nucleus present in theazo dyestufi.

Diazotisation of amines of the above formulae may be convenientlybrought about by adding sodium nitrite to a solution or suspension ofthe aromatic or heterocyclic amine in an aqueous solution of an acid forexample hydrochloric acid and the diazo solution or suspension obtainedmay then be added to a solution of the coupling component in a suitablesolvent for example water, the pH of the mixture being adjusted toensure that coupling takes place at a convenient rate. Thewater-insoluble azo dyestutf which is precipitated may then be filteredoff. When the coupling is carried out in the presence of a solvent forthe water-insoluble azo dyestuif, for example acetone, the dyestufi ispreferably isolated by adding water until all the dyestuif has beenprecipitated.

As examples of amines of the above formulae there may be mentioned 2-,3- or 4-aminobenzenesulphon-N (B- chloroethyDarnide 2-, 3- or4-aminobenzenesulphon-N- (,B-bromoethyDamide, Z-aminobenzenesulphon N('ychloroprop-fl-yDamide, 3-chloro-4-aminobenzenesulphon-N-(;8-chloroethyl)amide, 2:5-dichloro-4 aminobenzenesulphon-N-,B-chloroethyl) amide, 2-naphthylamine-6-sulphon-N-(B-chloroethyl)amide,3- or 4-aminobenzenesulphon-N-(fl-chloroethyl)methylamide, 2-, 3- or4-aminobenzenesulphon-N-(B-chloroethyl)phenylamide, 2-, 3- or4-aminobenzenesulphon-N-(v-chloro-B hydroxypropyl) phenylamide, 2-, 3-or 4-aminobenzenesulphon N (2- chlorocyclohexyl)amide, 2-, 3- or4-aminobenzenesulphon- N- 3-chloropiperidyl) amide, 2:S-dimethoxy-4-aminoazobenzene-3'-sulphon-N-(li-chloroethyl)amide,aniline, rnor p-toluidine, 0, m, or p-chloroaniline, o, m, orpnitroaniline, 3-chloro 4 aminophenylmethylsulphone, o, m, orpanisidine, 5-nitro-2-arnino thiazole, 6-ethoxy-2- aminebenzthiazole,Z-amino-5-nitrobenZenesulphon-N-(,6- chloroethyl)amide,6-methylsulphonyl-2 aminobenzthiazole m-aminobenzotrifiuoride,4-aminobenzonitrile, 2-carbomethoxyaniline, p-aminoacetanilide,2:5-dimethoxyaniline, aor B-naphthylamine, l-naphthylaminetor 5-su1-phon-N- B-chloroethyl) amide, and 4-aminoazobenzene.

Amines of the above formulae which contain an SO NRR' group ashereinbefore defined may be obtained from the corresponding amines whichcontains a sulphonic acid group by acetylating the amino group,converting the sulphonic acid to the corresponding sulphonchloride,subsequently reacting with an amine of the formula: NHRR' where R and Rhave the meanings stated above and finally hydrolysing off the N-acetylgroup. Alternatively such amines may be obtained from the correspondingnitro sulphonic acids by converting to the sulphonchloride, reactingwith an amine of the formula: NHRR where R and R have the meaningsstated above and subsequently reducing the nitro group to an aminogroup.

As examples of coupling components which may be used in the manufactureof the new water-insoluble azo dyestuffs there may be mentioned phenols,for example phenol, p-cresol and p-phenylphenol, naphthols, for example,B-naphthol and 2-naphthol-6-sulphon-N-(fi-chloroethyl)amide,arylamines, for example N-ethyLN-B-hydroxyethylaniline, B-methyI-N:N-di(,6 hydroxyethyl)aniline, Z-methoxy-S-methyl-N N-di(fl-hydroxyethyl) aniline, N-B-hydroxyethyl-l-naphthylamine,Z-naphthylamine 6- sulphon-N- ,B-chloroethyl) amine, N-fl-cyanoethyl-l-naphthylamine, 3-methyl-N-(,B-hydroxyethyl)-N ([3 cyanoethyl) aniline,3-N N -diethylaminobenzenesulphon-N- flchloroethyl)amide, pyrazolones,for example 3-methyl-5- pyrazolone, 3-carbethoxy-S-pyrazolone, 1-[3-(/3chloroethyl) aminosulphonylphenyl] 3-methyl-5-pyrazolone, andacetoacetylaminobenzene compounds, for example acetoacetanilide and3-acetoacetylaminobenzenesulphon-N-(B- chloroethyl) amide.

Phenols and naphthols which contain an -SO NRR group, as hereinbeforedefined, may be obtained from the corresponding phenol or naphtholsulphonic acids by treating with p-toluenesulphonylchloride, reactingthe O-p-toluenesulphonyl derivative so obtained with phosphoruspentachloride, treating the sulphon chloride so obtained with an amineof the formula: HNRR' where R and R have the meanings stated above, andsubsequently hydrolysing off the O-p-toluenesulphonyl group.

Arylamines which contain an SO NRR group, as hereinbefore defined, maybe obtained by converting the corresponding arylamine sulphonic acid tothe sulphonchloride and subsequently treating with an amine of theformula: I-INRR where R and R have the meanings stated above.

Pyrazolones which contain an SO NRR group, as hereinbefore defined, maybe obtained from the corresponding aromatic amines containing the -SONRR' group by diazotising, reducing to the hydrazine, condensing withethylacetoacetate or acetoacetamide and ring closing.

Acetoacetylaminobenzene compounds which contain an SO NRR group ashereinbefore defined may be obtained from the corresponding aromaticamine containing the SO NRR' group by reacting the aromatic amine withdiketene.

Alternatively the water-insoluble dyestutfs of the invention may bemanufactured by converting the corresponding azo compound containing oneor more sulphonic acid groups to the sulphonchloride and subsequentlytreating with an amine of the formula: HNRR where R and R have themeanings stated above.

Azo compounds containing one or more sulphonic acid groups used in thisalternative process may be obtained, by coupling diazotised primaryaromatic or heterocyclic amines with coupling components, the aromaticor heterocyclic amines and coupling components being so chosen that theresultant azo compounds are water-insoluble as aforesaid and contain atmost one radical of the formula and one or two 50 E groups each of whichis directly attached to a different aryl nucleus.

sion of an aforesaid amine of the formula A-NH or A-(N=NA) -NH inconjunction with a treatment with aqueous nitrous acid, the couplingcomponent and the amine being so chosen that the resultant dyestuf'rcontains one or two groups of the formula --SO NRR as hereinbeforedefined, contains at most one radical of the formula and iswater-insoluble as aforesaid.

The new water-insoluble azo dyestuffs as hereinbefore defined may beused for the colouration of textile materials comprising animal fibressuch as wool, silk and regenerated protein fibres, and artificial fibressuch as cellulose ester fibres for example secondary cellulose acetateand cellulose triacetate fibres, synthetic linear polyamide fibres,especially polyhexamethylene adipamide and polycaprolactam,polyurethane, polyester, polyacrylonitrile and modifiedpolyacrylonitrile fibres, by treating the textile materials with aqueousdispersions of the dyestuffs. The aqueous dispersions of the dyestuffsmay be obtained by methods known and described for disperse dyestuffs ingeneral, for example by milling with the aid of dispersing agents forexample the sodium salt of sulphonated naphthalene formaldehydecondensation products with or without the addition of protectivecolloids for example dextrin. The dyestuffs may if desired be convertedinto a dispersible powder form. Substances known to assist or improvedyeing, for example the dispersing agents and protective colloidsdescribed above and electrolytes, may be added to the dyebath.

The dyestuffs may be applied to the textile materials at a temperatureat or near the boiling point of the dyebath, preferably at a temperaturebetween 75 C. and 100 C., or if desired, a higher temperature forexample a temperature between 100 C. and 130 C. may be used atsuperatmospheric pressure. Textile materials which are not stable attemperatures above 90 C., for example secondary cellulose acetate, arepreferably dyed at temperatures between 60 C. and 85 C.

In the dyeing of cellulose triacetate or polyester textile materialswith the dyestuffs of this invention it is sometimes advantageous to usea swelling agent or other carrier material for example diphenyl,dichlorobenzene, or trichloroethylene.

The new water-insoluble dyestuffs may also be applied to textilematerials in the form of a thickened printing paste containing a finedispersion of the dyestuff. The printing paste may be thickened with anyof the usual thickening agents for example with methyl cellulose,starch, locust bean gum, Nafka crystal gum, or sodium alginate, and maycontain normal adjuvants for printing pastes such as urea, thiourea orthiodiglycol, adjuvants for the application of disperse dyes such asmethylated spirits, sodium meta-nitrobenzenesulphonate or aqueousemulsions of sulphonated oils, swelling agents or dyeing carriers suchas diphenyl.

The printing paste may be conveniently applied to the textile materialsby printing with block, spray, stencil, screen or roller, preferablydrying the printed materials and if desired steaming at superatmosphericpressure, when a temperature above 100 C., preferably between 110 C. and130 C., is required.

The new water-insoluble azo dyestufis are of especial value for printingcellulose acetate textile materials.

If desired the water-insoluble azo dyestuffs, as hereinbefore defined,may be applied to artificial textile materials in conjunction with atreatment with an amine, phenol or thiophenol, which may be applied tothe textile material prior to, simultaneously with or subsequent to theapplication of the dyestufi.

When used on textile materials comprising wool, silk or regeneratedprotein fibres or artificial fibres such as polyamide fibres orbasically modified polyacrylonitrile fibres the new water-insoluble azodyestuffs, as hereinbefore defined, give colourations distinguished bytheir high fastness to Wet treatments and to dry heat. They also haveexcellent dyeing properties, especially build-up and levellingproperties, and on this account they are of great value for applicationto barr nylon. In many cases also the new water-insoluble dyes haveexcellent fastness to light.

A preferred class of the new water-insoluble azo dyestufls, ashereinbefore defined, are those azo dyestuffs in which R represents aB-chloroethyl or a B-bromoethyl radical and R represents a hydrogenatom, that is to say in which SO NRR is representative of asulphon-N-(B- chloroethyl) amide or a sulphon-N-(fl-bromoethyl) amidegroup.

As examples of this preferred class of the new waterinsoluble azodyestuff, as hereinbefore defined, there may be mentioned the dyestuffsof the formula wherein Y is selected from the class consisting ofchlorine and bromine, X is selected from the class consisting ofhydrogen, chlorine, and bromine, B represents a member selected from theclass consisting of a benzene and a naphthalene radical, and D isselected from the class consisting of a primary amino, a secondaryamino, and a tertiary amino group.

The benzene or naphthalene radical represented by B may carrysubstitutents, for example alkyl such as methyl, trifluoromethyl, alkoxysuch as methoxy, halogen such as chlorine and bromine, and acidylaminosuch as acetylamino.

As examples of the primary, secondary and tertiary amino groups whichmay be represented by D there may be mentioned methylamino, ethylamino,fi-hydroxyethylamino, fi-cyanoethylamino, dimethylamino, diethylamino,di (ethoxyethyl)amino, methyl B hydroxyethylamino,ethyl-B-hydroxyethylamino, fl-cyanoethyl-B-hydroxyethylamino,,8-cyanoethyl-fl-methoxyethylamino, ethyl-flz' -dihydroxypropylamino andbutyl-B-hydroxyethylamino, and as examples of the halogen atomsrepresented by X there may be mentioned chlorine and bromine.

When applied to textile materials, the dyestuffs of this formula giveorange to violet shades which are nonphototropic and possess excellentfastness to light, to wet treatments and to dry heat. They haveexcellent dyeing properties on polyamide and cellulose ester textilematerials.

As further examples of the preferred class of waterinsoluble azodyestuffs, as hereinbefore defined, there may be mentioned dyestufls ofthe formula wherein P represents a member selected from the classconsisting of a benzene, naphthalene, thiazole, and benzthiazoleradical, Y is selected from the class consisting of a chlorine and abromine atom, and Z represents a tertiary amino group.

As specific examples of the radicals represented by P there may bementioned p-nitrophenyl, 2-chloro-4-nitrophenyl, p sulphonarnidophenyl,2 chloro 4 ethylsulphonylphenyl, 4 cyano 2 trifluoromethylphenyl, cyano4 nitrophenyl, 4 nitro 2 trifluoromethylphenyl, 2 chloro 4 ,8hydroxyethylsulphonylphenyl, 5 nitrothiazole 2 yl, 6 nitrobenzthiazole 2yl, 6- methylsulphonyl benzthiazole 2 yl, and 6 sulphamyl- 2-naphthyl.

As examples of tertiary amino groups represented by Z we may mentiondimethylarnino, diethylamino, dibutylamino, di ([3 hydroxyethyl)amino, Nethyl N flhydroxyethylamino, N:N di (e cyanoethyl)amino,

N ,8 hydroxyethyl N [3' cyanoethylamino, NzN- di (B methoxyethyl)aminoand B methoxyethyl N- fl'-cyanoethylamino.

When applied to artificial textile materials comprising polyamidefibres, the dyestuffs of the above formula give orange to blue shadespossessing excellent fastness to Wet treatments and to dry heat. Theyalso have excellent dyeing properties.

As further examples of the preferred class of the new water-insolubleazo dyestuffs, as hereinbefore defined, there may be mentioned the azodyestuffs of the formula wherein B and B each represent a benzeneradical, Y is selected from the class consisting of a chlorine and abromine atom, and the OH group is attached to B ortho to the N=N- link.

The benzene radicals B and B may carry substituents for example halogensuch as chloro and bromine, alkyl such as methyl and tert-butyl, alkoxysuch as methoxy, and aryl such as phenyl.

When applied to artificial textile materials the dyestuffs of the aboveformula give yellow shades which are non-phototropic and which haveexcellent fastness to wet treatments, to light and to dry heat. Theyalso have excellent dyeing properties on polyamide and cellulose acetatetextile materials.

As further examples of the preferred class of the new water-insolubleazo dyestuffs, as hereinbefore defined, there may be mentioned thedyestuffs of the formula wherein B and B each represent a benzeneradical and Y is selected from the class consisting of a chlorine and abromine atom.

The benzene rings B and B may carry substituents for example halogensuch as chlorine or bromine, alkyl such as methyl, alkoxy such asmethoxy, trifiuoromethyl, sulphonamido or substituted sulphonamido suchas sulphon- (,8-hydroxyethyl)amido, and acidylamino such as acetylaminobut it is preferred that the benzene ring is substituted by an alkylgroup or a halogen atom in the 2 position.

When applied to artificial textile materials the dyestuffs of the aboveformula give greenish yellow shades possessing excellent fastness to wettreatments and to light.

The invention is illustrated but not limited by the following examplesin which the parts and percentages are by weight.

Example 1 A solution of 6.9 parts of sodium nitrite in 50 parts of wateris added gradually to a solution of 27.1 parts of4-aminobenzenesulphon-N- (fi-chloroethyl amide hydro chloride in amixture of 400 parts of water and 15 parts of a 36% aqueous solution ofhydrochloric acid at a temperature between 15 C. and 20 C. The solutionso obtained is added during 20 minutes to a solution of 16.5 parts ofN-ethyl-N-beta-hydroxyethylaniline in a mixture of 200 parts of waterand 11.2 parts of a 36% aqueous solution of hydrochloric acid at atemperature between C. and C. After stirring the mixture for 2 hours itis neutralised to Congo red by adding 55 parts of a 30% aqueous solutionof sodium acetate slowly over 30 min utes. After 5 minutes the insoluble4-(l3-chloroethyl) aminosulphonyl-4-N-ethyl-N-(Ii-hydroxyethyl)aminoazo-benzene is filtered off, washed with water and dried.

1 part of the product so obtained is dispersed in parts of water bymilling in the presence of a sodium salt of a sulphonated naphthaleneformaldehyde condensation product and the dispersion so obtained isadded to 4,000 parts of water containing 4 parts of a condensate ofethylene oxide with a fatty alcohol. 100 parts of nylon (polyamide)textile material are placed in the dyebath so obtained and the dyebathis then heated to C. and maintained at that temperature for 60 minutes.The nylon fabric is then rinsed in water, immersed for 30 minutes in ahot aqueous solution containing 0.2% of sodium carbonate and 0.1% of acondensate of ethylene oxide with an alkyl phenol, again rinsed withWater and dried. The polyamide textile material is dyed to an orangeshade of very good fastness to washing.

Polyhexamethylene adipamide or palycaproiactam may be used as the nylon(polyamide) textile material in this example and throughout thefollowing examples.

If the polyamide textile material is replaced by parts of secondarycellulose acetate and the dyebath is heated at 85 C. for 60 minutes thecellulose acetate is dyed to an orange shade.

Example 2 The 16.5 parts of N-ethyl-N-B-hydroxyethylaniline used inExample 1 is replaced by 19.5 parts of N:N-di-(B- hydroxyethyl)m-toluidine. 4-(B-chloroethyl)aminosulphonyl-2-methyl-4-N N-di{B-hydroxyethyl) aminoazo benzene is obtained which dyes secondarycellulose acetate in orange shades and polyamide textile materials inorange shades of very good fastness to washing.

The degree of fixation of the dyestuff on the dyed nylon is determinedas follows:

The dyed polyamide textile material is successively extracted withn-propanol at 85 C. until no more dyestuff is removed from the nylon onfurther treatment with n-propanol. The quantity of dyestuff remaining inthe polyamide textile material is then found by dissolving the polyamidetextile material in o-chlorophenol and determining the dyestuifcolorimetrically. Comparison with the quantity of dyestuif found in thesame way to be present in an identical weight of similarly dyedpolyamide textile material before extraction with n-propanol gives thedegree of fixation as 69%.

In a similar test on polyamide textile material dyed with4-(beta-hydroxyethyl)-aminosulphonyl-2-methyl-4'-NzN-di(beta-hydroxyethyl)aminoazobenzene the whole of the dyestulf wasextracted by the n-propanol at 85 C.

The following table contains further examples of dyestufis prepared byinteracting diazotised 4-aminobenzene sulphon-N-(beta-chloroethyl)amidewith arylamine coupling components according to the method of Example 1.

Shade on Ex- Coupling Component Polyamide ample Textile Materials 3NzN-di-(2-hydroxyethyl)amino-Z-methoxy-S- Reddisbmethylbenzene. orange.4 N-2-hydr0xyethyl-N-2-aminoethylaniline Redillishye ow. 5N-Z-hydroxethyl-N-2-eyanoethyl-m-toluldlne Yellowishorange. 6N-2hydroxyethyl-alpha-naphthylamine Red. 7N-betarhydroxyethyl-2-naphthylamine Briggit re 8N:N-di(beta-hydroxyethyl)aniline Orange. 9N-beta-hydroxyethyl-N-beta-cyanoethylaniline. Redillishye ow. 103-N:Ndiethylaminobenzenesulphon-N-(beta- Orange.

ehloroethyDamide. 11 2-naphthylarnine-G-sulphonamide Do. 122-naphthylaminefisulphon-N-(beta-ehloro- Do.

ethyl) amide. 13 3-hydr0xy-1:2:3:4-tetrahydro-7z8-1:2-benz0- Rubine.

quinoline. 14 2-N:N-di(beta-hydroxyethyl)amino 4-aeety1z Red.

minoanisole. 15 l-N-beta-hydroxyethylamino-S:8-dlchloro- Do.

naphthalene. 16 Lid-beta-hydroxyethylaminoA-chloronaphtha- Pink.

ene. 17 2ethoxy-1-naphthy1amine 131111511- re 185:6:7:8-tetrahydro-1-N:N-di-(beta-hydroxy- Orange.

ethyDnaphthylamine.

9 The fixation on the polyamide textile material was 74% in the case ofExample 5 and 70% in the case of Example 6. 1

Example 19 30.55 parts of3-chloro-4-aminobenzenesulphon-N-betachloroethylamide hydrochloride aredissolved by warming in a mixture of 200 parts of acetic acid and 15parts of a 36% aqueous solution of hydrochloric acid and the solutioncooled to a temperature between 15 C. and 20 C. To the suspension soobtained is added over 10 minutes a solution of 6.9 parts of sodiumnitride in 50 parts of water. 200 parts of water are then added and theresulting suspension of diazonium compound is added over 20 minutes to asolution of 19.5 parts of NzN- di(beta-hydroxyethyl)-m-toluidine in amixture of 180 parts of Water and 18 parts of a 36% aqueous solution ofhydrochloric acid at a temperature between C. and 5 C. The mixture isstirred for 30 minutes, neutralised to Congo red by slowly adding 70parts of a 30% aqueous solution of sodium acetate and then stirred for afurther 5 minutes. 2 chloro 4 (beta chloroethyl) aminosulphonyl-2-methyl4'-N:N di(beta-hydroxyethyl)aminoazobenzene so obtained is then filteredoff, washed with water and dried. When dispersed in aqueous medium itdyes secondary cellulose acetate to reddish-orange shades and polyamidetextile materials to scarlet shades of very good fastness to washing.

The fixation of the dyestuif on the dyed nylon is 69%.

Example 20 A solution of 6.9 parts of sodium nitrite in 50 parts ofwater is added gradually to a solution at C. of 27.1 parts of3-aminobenzenesulphon N (beta chloroethyl)amide hydrochloride in amixture of 480 parts of water and parts of a 36% aqueous solution ofhydrochloric acid. The solution so obtained is added during 10 minutesto a solution of 10.9 parts of p-cresol and 10.8 parts of sodiumcarbonate in a mixture of 240 parts of water and 8 parts of a 32%aqueous solution of sodium hydroxide solution at 0 C. The3-(beta-chloroethyl)- aminosulphonyl 2'-hydroxy- 5'-methylazobenzene isfiltered oif, washed with water and dried. When dispersed in aqueousmedium it dyes polyamide textile materials in yellow shades of goodfastness to washing.

The following table gives the shades on polyamide textile materials ofthe dyestuffs obtained by similarly coupling diazotised4-aminobenzenesulphon-N-(beta-chloroethyl)amide with the couplingcomponents specified in the second column of the table.

Example 32 The 10.9 parts of p-cresol used in Example are replaced by16.1 parts of 2:4-dihydroxyquinoline. A dyestufl is obtained which dyespolyamide textile materials in greenish-yellow shades of good fastnessto washing.

Example 33 27.1 parts of 3-aminobenzenesulphon-N-(beta-chloroethyl)amidehydrochloride are diazotised as in Example 20 and the resulting solutionis added during 10 minutes to a solution of 15.3 parts of2:5-dimethoxyaniline in a mixture of 200 parts of water and 10 parts ofa 36% aqueous solution of hydrochloric acid at a temperature of between0 C. and 5 C. After 12 hours the insoluble product is filtered oil andthen stirred into a mixture of 1200 parts of water and 25 parts of a 36%aqueous solution of hydrochloric acid. A solution of 6.9 parts of sodiumnitrite in 50 parts of water is then added at 10 C. and the mixturestirred for 4 hours. The mixture so obtained is added to a solution of9.4 parts of phenol and 16.0 parts of sodium carbonate in a mixture of40 0 parts of water and 8 parts of a 32% aqueous solution of sodiumhydroxide solution at a temperature between 0 C. and 5 C. The diazocompound so obtained is filtered off, washed with water and dried. Whendispersed in aqueous medium it dyes polyamide textile materials inorange shades of good fastness to washing.

Example 34 27.1 parts of S-aminobenzenesulphon-N-(beta-chloroethyl)amide hydrochloride are diazotised according to the method ofExample 20 and the resulting solution is added during 10 minutes to asolution of 18.1 parts of N:N-di(beta-hydroxyethyl)aniline in a mixtureof 200 parts of water and 10 parts of a 36% aqueous solution ofhydrochloric acid at a temperature of between 0 C. and 5 C. The mixtureis neutralised to Congo red by the addition of 50 parts of a 30% aqueoussolution of sodium acetate and after 12 hours the resulting dye isfiltered oil, washed with water and dried. When dispersed in aqueousmedium it dyes polyamide textile materials in orange shades of goodfastness to Washing.

Example 35 The 18.1 parts of NzN di(beta hydroxyethyl)aniline used inExample 34 are replaced by 19.5 parts of NzN- di (beta-hyd roxyethyl-m-toluidine. 3 (beta-chloroethyl) aminosulphonyl-2-methyl-4-N N-di(beta-hydroxyethyl) aminoazobenzene is obtained which dyes polyamidetextile materials in orange shades of good fastness to washing.

Example 36 27.1 parts of 4-aminobenzenesulphon-N-(beta-chloroethyl)amidehydrochloride are diazotised according to the method of Example 1 andthe resulting solution is added during 20 minutes to a solution of 19.9parts of N-betacyanoethyl-alpha-naphthylamine in 800 parts of acetone ata temperature between 0 C. and 5 C. The mixture is stirred for minutesand then neutralised to Congo red by slowly adding 25 parts of a 30%aqueous solution of sodium acetate. The dyestuff is filtered ofi',washed with water and dried. When dispersed in aqueous medium it dyescellulose acetate rayon in orange shades and polyamide textile materialsin scarlet shades of very good fastness to washing. The fixation of thedyestuff on the dyed polyamide textile material is 68%.

Example 37 A solution of 6.9 parts of sodium nitrite in 50 parts ofwater is added to a solution of 27.1 parts of Z-aminoben- Zenesulphon N(beta-chloroethyl) amide hydrochloride in a mixture of parts of aceticacid and 4 parts of a 36% aqueous solution of hydrochloric acid at atemperature between 10 C. and 15 C. The solution is stirred for 15minutes and then added during 20 minutes to a solution of 19.5 parts ofNzN-di(beta-hydroxyethyl)-mtoluidine in a mixture of 200 parts of waterand 12 parts of a 36% aqueous solution of hydrochloric acid at atemperature of between 0 and 5 C. The mixture is stirred for 2 hours andthen neutralised to Congo red by slowly 11 adding 40 parts of a 30%aqueous solution of sodium acetate. The dyestuff is filtered off, washedand dried. When dispersed in aqueous medium it dyes polyamide textilematerials in orange shades of excellent fastness to washing and wool inorange shades of good fastness to washing and milling.

Example 38 The 27.1 parts of 2 aminobenzenesulphon N(betachloroethyl)amide hydrochloride used in Example 14 are replaced by28.5 parts of 2-aminobenzenesulphon-N-(gamma-chloroprop-Z-yl)amidehydrochloride. A dyestuff is obtained which dyes polyamide textilematerials in orange shades of very good fastness to washing, and wool inorange shades of good fastness to waslnng and milling.

Example 39 A solution of 6.9 parts of sodium nitrite in 50 parts ofwater is added during minutes to a solution of 30.1 parts of 4aminobenzeuesulphon-N-(gamma-chloro-betahydroxypropyl)amidehydrochloride in a mixture of 375 parts of water and 15 parts of a 36%aqueous solution of hydrochloric acid at a temperature of between 5 andC. The solution so obtained is added during 20 minutes to a solution of19.5 parts of N:N-di-(beta-hydroxyethyD- m-toluidine in 250 parts ofwater and parts of a 36% aqueous solution of hydrochloric acid at atemperature of between 0 and 5 C. After stirring the mixture for 2 hoursit is neutralised to Congo red by adding 62.5 parts of a 30% aqueoussolution of sodium acetate slowly over 30 minu The insoluble product isfiltered off, stirred for 30 minutes in 400 parts of water which havebeen made alkaline to litmus by the addition of sodium carbonate,filtered off, washed with water and dried. 4-(gammachloro betahydroxypropyl)aminosulphon 2' methyl-4'-N:N-di(beta-hydroxyethyl)aminoazobenzene is obtained which has verygood build-up properties on polyamide textile materials giving orangeshades of good fastness to washing.

Example 40 30.1 parts of4-aminoben1enesulphon-N-(gammachloro-beta-hydroxypropyl)amidehydrochloride are diazotised as in Example 39 and the solution soobtained is added over minutes to a solution of 10.8 parts of p-cresolin a mixture of 300 parts of water, 50 parts of a 2 N aqueous solutionof sodium hydroxide and 75 parts of a 2 N aqueous solution of sodiumcarbonate at a temperature of between 5 C. and 10 C. The mixture isstirred for 1 hour and the insoluble product filtered oflF, washed withwater and dried. 4(gamma-chloro-beta-hydroxypropyl)aminosulphon 2'hydroxy-5'-methylazobenzene is obtained which dyes polyamide textilematerials in yellow shades of good fastness to washing.

Example 41 A solution of 6.9 parts of sodium nitrite in 50 parts ofwater is added gradually to a suspension of 26.9 parts of 4-amino 3chlorobenzene sulphon-N-(beta-chloroethyl) amide in a mixture of 400parts of water and parts of a 36% aqueous solution of hydrochloric acidat a temperature between 5 C. and 10 C. The suspension so obtained isthen added during 20 minutes to a solution of 19.6 parts ofN-beta-cyanoethyl-alpha-naphthylamine in a mixture of 512 parts ofacetone and 12 parts of a 36% aqueous solution of hydrochloric acid at atemperature of between 0 C. and 5 C. The mixture is stirred for 2%hours, 68 parts of a aqueous solution of sodium acetate are added, themixture then stirred for a further 16 hours, 6 parts of the sodiumacetate solution added. The precipitated dyestuif is then filtered ofi,washed with water and dried. When dispersed in aqueous medium it dyespolyamide textile materials in red shades possessing excellent fastnessto washing.

The following table gaves the shade on polyamide textile materials ofthe dyestuffs obtained by similarly coupling diazotised4-amino-3-chlorobenzenesulphon-N- (beta-chloroethyDamide with thecoupling components specified in the second column of the table.

Shade on Ex- Coupling Component Polyamide ample Textile MaterialsN:N-di(beta hydroxyethyl)eresidine Red.N-beta-hydroxyethyi-N-beta-eyanoe thyl Orange.

aniline. N-n-butyl-N-beta-hydroxyethyl-m-tolui dine Scarlet.N-beta-hydroxyethyl-alpha-naphthylaminc Maroon.N-beta-hydroxyethyl-N-beta-eyanoethyl-m- Reddishtoluidine. orange.3-NzN-dimothylaminobenzenesulphon N-(beta- ReddishchloroethyDamide.orange. N-beta-hydroxyethyl-Z-naphthylamine Red. N N -di(bota-hydroxyethyl) aniline Reddishoran e.2-N:N-di(beta-hydroxyethyl)amino-hace'tyla- Blnish minoanisole. red.lethoxy-Lnaphthylamine Reddishviolet.

52 4-ehloro-l-N-(beta-hydroxyethyl)-naphthyl- Bluishamine. red.

53 5:6:7:B-tetrahydro-l-N:N-di(beta-hydroxy- Orange.

ethyDnaphthylamine.

54 N-betu-ethoxyethyl-N-beta-eyauoethyl-m- Do.

toluidine.

The following table gives the shade on polyamide textile materials ofother dyestuffs which are obtained by diazotising the amines listed inthe second column of the table and coupling the diazo compounds soobtained with the coupling components hsted 1n the third column of thetable. The diazotisation of the amines and the subsequent coupling withthe coupling components were carried out by the methods described in theprevious examples.

' Shade on Ex- Amine Coupling Component Polyamide ample TextileMaterials 55 2 a1ninobenzenesul- 3-metliy1-5-pyrazo1one. Yellow,

phon-N-(betaehloroethyhamide.

5G 28.11151dlne-d-SulphOll- N:N-di(beta-hydroxy- Orange,N-(gamrna-ehloroeLl1y1)-m-toluidine. beta-hydroxypropyl) amide.

57 2-anisidine-4-sulphon- N-beta-hydroxyethyl- R d,

N-(beta-cl11oroetl1yl) l-naphthylamine. amide.

58 3-aminohenzenesulp-Cresol Grcenishphon-N-(g yellow.ehloro-beta-hydroxypropybamide.

59 3-aminobenzensul- 3-hydroxy-7z8-benz- Red,

phon-N-(gamma- 1 2:3: 4-tetrahydrochloro-beta-hydroxyquinoline.propyD-N-methylamide.

60 3-aminobenzenesulp-Cresol Yell w,

ph0n-N-(gammaehloro-beta-hydroxypropyl)anilide.

61 3-aminobenzenesul- .do D

phon-N-(2-chloroeyelohexybamide.

62 4-aminobenzenesul- N:N-di(beta-hydroxy- Orangc phon-N-(beta:ethyD-m-toluidinc. gamms-di-ehloropropyDamide.

63 2-amino-4-trifluor0- do Scar-1 mmethylbenzenesulplion-N-(betaehloroetliyl) amide.

64 2-amino-5-nitroben- .do Reddi hzenesulphon-N- violet,(bets-ehloroethyl) amide.

65 i-aminobenzenesul- .d0 Orange,

phon-N-(gammabromo-beta-hydroxypmpyDamide.

66 4arninobenzenesuld0 Do,

phon-N-(betnbromoethyDamide.

67 p-Nitroaniline Z-naphthol-G-sulphon- Reddish- N-(beta-chloroethyl)orange. amide.

68 do Z-naphthol-G-sulphon- D N-(gamina-ehlorobeta-hydroxypropyl) amide.

Shade on Shade on Ex- Amine Coupling Component Polyaniide Ex- AmineCoupling Component Polyamide ample Textile ample Textile MaterialsMaterials 69 p-Aminobenzenesul- 2naphthylamine-6- Orange. 1054-aminobenzenesulp-Gresol Yellow.

phonainide. sulphon-N-(betaphon-3-chlorochloi'octhybamide. piperidide.

70 p-Nitroaniline 3-NzN-diethylamino- Red. 106 Sulphanilamide 1-[3-(;3-ehlor0ethyl- Do.

benzenesulphon-N- aminosulphonyl- 2(lllileitgcliloroethyl) 1ogggizygllgiggiethyl-s- 2'chloro-4-nitr0aniline d Bluish-red. 107"---2-amino-4-methylthia- 3-NzN-diethylamino- Orange. p-Aminobenzenesul-Orange. zole. benzenesulphon N- plionamide. B-chloroethyla-mide.3-chloro-4-aminophen- Scarlet. 108 2-amino-5methyll-naphthylarninei- Do.

2 yle thyl5sulphole. R d sulphonylthiazole. ziliillglligrrlil-ilge-fi-chloroalIIllIlO- -cyan0 61120 e trifluoride.2-amino-5-nitrobenzo- Reddishnitrile. violet. 2%1'nf'1510-5fi1it10b0n20-Bluish-red.

ri uori e. a v v fi Scarlet The 2-anisidine-4-sulphon-N-(fl-chloroethyl)amide used 5, gE.;5gi in the above examples may be obtained by treatingacetyl- 78 i i 3 Z-anisidine with chlorosulphonic acid and reacting the79 Ilene" if ifii tfgfifii l e resultingacetyl-Z-anisidine-4-sulphonchloride with betalgy chloroethylamine in a10% aqueous solution of acetone,

80 3 i b 1 fii fi Do the mixture being kept neutral to litmus by theaddition of g 'i th 1 sodium carbonate, filtering off the acetyl2-anisidine-4- 553? 3 )me ysulphon-N-(beta-chloroethyl)amide which isformed and Orange heating this with a 15% aqueous solution ofhydrochloric S I) 011- chlpmthynamme, toluidine, acid at 80 C. Thesolution is then cooled and the 2- 8 RF fgg i gi fgg g anisidine 4sulphon-N-(beta-chloroethyl)amide hydro- 83 i -i P ;g l- Yellow- The2-amino-4-trifluoromethylbenzenesulphon-N-(betaowe y chloroethyl) amideused in the above examples may be ob- 84 g i 'figggg tained by reacting2-nitro-4-trifluoromethylchlorobenzene 85 4-aminobenzenesu1- -cr 1Yeilow, with sodium disulphide, passing chlorine into an aqueous g z gg'gifg suspension of the 2:2'-dinitro-4:4'-di(trifluoromethyl)- di h ldiul hid obtained reactin the 2-nitro-4-tripropyDamide. P y S P e 30 a g86 N'beta'hydmxyithyl' Blmsh'redfluoromethylbenzenesulphon chloride soobtained with methyl benzenesull-naphthylamme. b hl th I h d m eta-coroe yamine y roc on e in aqueous me ium $ggg UL p 0res01 Yellow in thepresence of Raney nickel catalyst, filtering on the 87 hon eta- 2nitro-4-trifluoromethylbenzenesulphon-i -(beta-ch1orobromoethybamide.ethy1)amide which is formed. This nitro compound is 4 do Do. 88 r 2ti1ord then reduced to the corresponding amino compound by ethy1)amide.hydrogenating an ethanol solution of the nitro compound 2-nahthol-fi-sul lion- Oran e.

89 p fifitfii N- metachiortgth i) g in the presence of Raney nicketcatalyst, filtering off the amide.

90 Hh10ro 2 trifiu0ro 2 naphthy]amme 6 D0 catalyst and evaporating oilthelethanol frlortrli the filttJrate methyl aniline, s iilphorilNfibetawhen 2 amino-4-trifiuoromethy benzenesu p on-N-( eta- Y chloroeth lamide is obtained in the form of an oil. 91 'gggfigfigf ggigb fgfli$""The 2 alnino-S-nitrobenzenesulphon N-(beta-chloro- 92 64 Bordeaux.'ethfylfiamide used in the above examples may be obtainedsulphon-N-(fl-chloroas O OWSZ eth Damide. i 93 2-ami1o-6methy1su l-N-ethyl-i -(3-fl-ch1oro- Bluish red. A olut.lon of 25 parts of beiiachloroethylmn? hydro phonylbenzthiazole.etllt'gylambnosilililphonchloride in 50 parts of Water is added withstirring to a y an solution of 40 parts of 4-nitroacetanilide2-sulphonylchlodo 3-N:N-diethylan1ino- Rubine. 2el%1ZlenSlt]il1p1110nlride (which is obtained by reacting 4-nitroacetamlide 2- 4} 01'06 Y amie.

95 N fl hyqmxyethyl N Bluishwi sulphonic acid with a mixture ofphosphorus oxychloride ethylsulphamyl) fi-a-mmocarb onyland phosphoruspentachloride) in a mixture of 160 parts Red of acetone and 40 parts ofwater, which has been cooled ethynaniline. to a temperature of 10 C. 170parts of a 2 N aqueous 97 Bemidme ggfgggggg ggeg solution of sodiumcarbonate are then added during 1 ethlylamide (2 hour and the mixturestirred for a further 20- hours, durmo es 9S Aminoazobenzene 2 naphthol6 smphon scarlet ing which time the acetone evaporates off. The precipi(v-ohloro-B -hydroxytatedZ-acetylammo-S-mtro-benzenesulphon-N-(beta-chlo- 99 MminobenzenesflYellow roethyl)amide is then filtered off, washed with Water andphon-N-(v-chloro-B- dried. A imxture of 20 parts of this compound, 38parts of water, 50 parts of acetone and 2 7 parts of a 36% 13-aniinobenzenesul- N:N-di-fly ynge. aqueous solution of hydrochloricacid 18 stirred at the boil g ggi ggg ggfiif ethyl'm'tolmdme' under areflux condenser for 8 hours. The solution is 3 benzylarm'de. ul a dr thI R d then cooled to 20 C. and the yellow crystalline solid 101 aminoenzenes y oxye y-ae naphthy1amme filtered off, washed with ater anddried. The product g g gg pyb-N- has a melting point of 125 C.

102 3-am i nobenzenesul- N:N-di-(fi-hydr oxy- Orange. 7 The 2-naphthol-G-sulphon-N-(beta-chloroethyl)amide Q ethyn'm'tolmdmeused inthe above examples may be obtained as follows:

eyclohexyDamide. 1Q3 3-aminohcnzenesulp-Cresol Yellow. A mixture of 23parts of 2-hydroxy-1-naphtho1c aci gfigg ggfi g6-sulphon-N-(beta-ehloroethyl)amide (which is obtained 104l-aminobenzenesul- N:N-cii(fi-hyd gw- Orangeby reactingZ-hydroxy-l-naphthoic acid 6-sulphonchloridephon-N-fl-'y-dibromoethyD-m-tolmdme. with beta-chloroethylamine in waterin the presence of propylamide.

sodium carbonate), 54 parts of water, 38 parts of a 36% aqueous solutionof hydrochloric acid and 80 parts of acetone is stirred at the boilunder a refiux condenser for 12 hours. The solution is then cooled to 20C. and the crystalline solid so obtained is filtered oif, washed withwater and dried. The product so obtained has a melting point of 137 C.

The 2 naphthylamine-6-sulphon-N-(beta-chloroethyl)- amide used in theabove examples may be obtained by re acting 2acetylaminonaphthalene-6-sulphonchloride with beta-chloroethylamine inwater in the presence of sodium carbonate, filtering off the2-acetylaminonaphthalene-6- sulphon-N-(beta-chloroethyl)amide which isprecipitated and hydrolysing oil? the N-acetyl group by heating thesolid so obtained with an aqueous solution of hydrochloric acid. Oncooling the solution the product crystallises out and is filtered offand dried.

1 naphthylamine-4-sulphon-N-(5 chloroethyl)amide may similarly beobtained from l-acetylaminonaphthalene-4-sulphonchloride andfl-chloroethylamine.

The 3-N:N-diethylaminobenzenesulphon-N-(,B-chloroethyl)amide used in theabove examples may be obtained by heating a mixture of 126 parts ofsodium diethyl metanilate and 583 parts of chlorosulphonic acid for 8hours at 100 C., pouring the mixture onto ice, filtering ofi the3-N:N-diethylaminobenzenesulphonchloride which is precipitated andreacting this with ,B-chloroethylamine in water in the presence ofsodium carbonate. The precipitated solid is then filtered off, washedwith water and dried. The product has a melting point of 62 C.

The 3 acetoacetylaminobenzenesulphon-N-(,B-chloroethyl)amide used in theabove examples may be obtained as follows:

A mixture of 12.6 parts of diketone, 23.5 parts of 3-aminobenzenesulphon-N-(B-chloroethyl)amide and 150 parts of,B-ethoxyethanol is stirred for 72 hours at 20 C., 500 parts of waterare then added and the precipitated solid is filtered ofi, washed withwater and dried. The product so obtatined has a melting point of 86 C.

The 3 aminobenzenesulphon-N-('y-chloro-fl-hydroxypropyl)-N-benzylamideand 3-aminobenzenesulphon-N-('y-chloro-B-hydroxypropyl-N-cyclohexylamide used in the above examplesmay be obtained by reaction of m-nitrobenzene sulphonchloride withbenzylamine and cyclohexylamine respectively, followed by condensationof the products with epichlorohydrin and reduction of the nitro group.

The 3 aminobenzenesulphon-N-('y-chloro-B-hydroxypropyl)-N-allylamideused in the above examples may be obtained by reaction ofm-acetylaminobenzenesulphon chloride with allylamine, followed bycondensation of the product with epichlorohydrin and hydrolysis of theacetyl rou g N ,B hydroxyethyl-N-fi'-arninocarbonyl ethyl-m-toluidine,used in the above examples may be obtained by the action of hydrogenperoxide on N-fi-hydroxyethyl-N-B- cyanoethyl-m-toluidine in alkalinemedium at a temperature of between 50 and 60 C.

N ethyl N (3 B chloroethylaminosulphonylbenzyl)aniline, used in theabove examples may be prepared by heating a mixture of 157 parts ofN-ethyl-N- (3'-sulphobenzyl)aniline (sodium salt) and 583 parts ofchlorosulphonic acid for 3 hours at 60 C., pouring the mixture onto ice,filtering off the N-ethyl-N-(3'-chlorosulphonylbenzyl)aniline which isprecipitated and reacting this with ,B-chloroethylarnine in water in thepresence of sodium carbonate. The precipitated solid is then filteredoil, washed With water and dried. The product has a melting point of7l72 C. 1-(3'-fi-chloroethyl aminosulphonylphenyl)-3-methyl-5-pyrazoloneused in the above examples may be prepared by reaction of 3-hydrazinobenzenesulphon N ([3 chloroethyl)amide (prepared fromm-aminobenzenesulphon-N-(,8-chloroethyl)amide via a Zinc/ acetic acidreduction of the diazosulphonate) with ethyl acetoacetate.

Example 109 A stirred solution of 2.91 parts of2-amino-6-(p-chloroethylsulphamyl)benzthiazole in 12 parts of phosphoricacid is cooled to 5 C. and 0.76 part of sodium nitrite is added evenlyduring 1 hour. 8 parts of glacial acetic acid is added and the mixturestirred for 5 to 10 minutes until there is no nitrous acid present. Asolution of 1.74 parts of 1-phenyl-3-methyl-5-pyrazolone dissolved in 4parts of glacial acetic acid is added to the mixture with stirring at 5to 10 C., followed by 11.3 parts of anhydrous sodium acetate. Themixture is stirred for 30 minutes then poured into parts of cold waterthe precipitated dyestuff filtered off and washed with water untilneutral. The dyestuli thus obtained dyed nylon in yellow shades.

2 amino 6 (3 chloroethylsulphamyl)benzthiazole may be obtained by theaction of bromine in glacial acid on a solution of4-aminobenzenesulphon-N-(fl-chloroethyl)amide and potassium thiocyanatein glacial acetic acid. The precipitate obtained is filtered 01f, boiledwith water, the solution obtained screened and neutralised while hotwith 4 N sodium acetate solution. The precipitated 2 amino 6 (5chloroethylsulphamyl) benzthiazole is filtered off, washed with Waterand dried. The product has a melting point of 191l92 C.

Example A solution of 6.9 parts of sodium nitrite in 50 parts of wateris added to a solution of 26.5 parts of Z-anisidine-4-sulphon-N-(B-chloroethyl)amide hydrochloride in a mixture of 600 partsof water and 15 parts of a 36% aqueous solution of hydrochloric acid,the temperature being held between 5 and 10 C. by external cooling. Thesolution so obtained is stirred for 10 minutes and then added to asolution of 13.7 parts of cresidine in a a mixture of 200 parts of waterand 12 parts of a 36% aqueous solution of hydrochloric acid at atemperature of between 5 and 10 C. The mixture is stirred for 2 /2 hoursand a 30% aqueous solution of sodium acetate added until the mixture isno longer acid to Congo Red. The amino monoazo compound so obtained isthen filtered off. The solid so obtained is then stirred with a mixtureof 1000 parts of water and 25 parts of a 36% aqueous solution ofhydrochloric acid, a solution of 6.9 parts of sodium nitrite in 50 partsof water is added the temperature of the mixture being held between 5and 10 C. by external cooling, and the mixture is then stirred at thistemperature for 17 hours. The solution so obtained is then added to asolution of 12.4 parts of m-methoxyphenol, 28 parts of sodium carbonate,40 parts of sodium acetate crystals and 4 parts of sodium hydroxide in450 parts of water, at a temperature of between 0 and 5 C. The mixtureis stirred for 30 minutes and the precipitated disazo dyestulf filteredoff, washed with water and dried. When the dyestuff is disperesed inaqueous medium it dyes polyamide textile materials in red shadespossessing excellent fastness to Washing.

Example 111 To a solution of 4.54 parts of 2-hydroxy-5-methyl-4'-aminoazobenzene in a mixture of parts of acetone and 100 parts of waterthere are simultaneously added a solution of 5.7 parts of3-(2'-chloroethyl)aminosulphonylbenzoylchloride in 16 parts of water and30 parts of an N aqueous solution of sodium carbonate, the temperatureof the mixture being maintained below 5 C. by external cooling. Themixture is then stirred for 20 hours, during which time the acetoneevaporates off. The precipitated dyestufi" is then filtered off, washedwith water and dried. When dispersed in aqueous medium it dyes polyamidetextile materials in yellow shades possessing excellent fastness towashing.

The 3 (2' chloroethyl)aminosulphonylbenzoylchlo- 17 ride used in theabove example may be obtained as follows:

A mixture of 20 parts of 3-(2-chloroethyl)aminosulphonyl benzoic acid(which is obtained by reacting benzoic acid 3-sulphonyl chloride withbeta-chloroethylamine), 13 parts of thionyl chloride and 80 parts oftoluene is stirred at the boil under a reflux condenser for 16 hours.The mixture is then distilled under reduced pressure until 50 parts ofdistillate are obtained. The residual liquid is then cooled and thesolid which crystallises out is filtered off, washed with toluene anddried. The product so obtained has a melting point of 82 6.

Example 1 12 1 part of the dyestuff of Example 19 is dispersed in 20parts of water and the dispersion so obtained is added to 4000 parts ofwater containing 4 parts of a condensate of ethylene oxide with a fattyalcohol. 100 parts of natural silk are placed in the dyebath so obtainedand dyeing is carried out for 1 hour at 95 C. The natural silk is thenremoved from the dyebath, rinsed in cold water, and then immersed for 15minutes in an aqueous solution containing 0.2% of a condensate ofethylene oxide with an alkyl phenol and 0.2% of sodium carbonate, whichis heated to 60 C. The natural silk is then rinsed in water and dried.The natural silk is dyed a scarlet shade possessing excellent fastnessto Wet treatments.

Example 1 13 In place of the 1 part of the dyestufi of Example 19 usedin Example 112 there is used 1 part of the dyestufi of Example 2 and inplace of the 100 parts of natural silk there are used 100 parts of amodified polyacrylonitrile fibre. The fibre is dyed an orange shadepossessing excellent fastness to Wet treatments.

Example 114 100 parts of polyhexamethylene adipamide textile materialare immersed in a dyebath comprising 4000 parts of Water and 5 parts ofZ-amino-5-nitrobenzenesulphon- N- (B-chloroethyDamide and the dyebath isthen heated at 85 C. for 1 hour. The textile material is then immersedfor 30 minutes in a mixture of 4000 parts of water, 12 parts of sodiumnitrite and 36 parts of a 36% aqueous solution of hydrochloric acid at15 C. The textile material is then removed from the mixture and immersedfor 30 minutes in a solution of 4 parts of 3-diethylaminoacetanilidehydrochloride in 4000 parts of water at C. The textile material is thenrinsed in water and treated for 30 minutes in a 0.2% aqueous solution ofsoap at C. The textile material is coloured a violet shade possessingexcellent fastness to wet treatments.

Example wherein:

R is a lower alkyl radical: P represents a radical selected from theclass consisting of thiazole and benzene radicals; and,

any substituents on the thiazole radical are selected from the classconsisting of methyl and nitro substituents, any substituents on thebenzene radical are selected from the class consisting of chlorine,nitro, sulphonamide, lower alkyl sulphonyl, cyano, trifluoromethyl,p-hydroxyethylsulphonyl, and sulphon N (B chloroethy1)- amidesubstituents.

No references cited.

1. DYESTUFFS HAVING THE FORMULA: